Organic conjugated compound with naphtho-ring Aza-BODIPY as basic skeleton and preparation method and application thereof

Abstract

The invention relates to the technical field of functional organic conjugated molecular materials, in particular to an organic conjugated compound with naphtho-ring Aza-BODIPY as a basic framework and a preparation method and application of the organic conjugated compound, the structure of the organic conjugated compound is shown as a formula (G): # imgabs0 #, R1 is alkyl; r2 is alkoxy, halogen or hydrogen; the invention overcomes the defects that in the prior art, the preparation process of Aza-BODIPY molecules with similar structures needs a complicated synthetic route, and various parallel ring structures are not easy to construct flexibly. The invention discloses an Aza-BODIPY molecule with a naphtho ring and a simple and convenient preparation method of the Aza-BODIPY molecule.

Description

Technical Field

[0001] The present invention relates to the technical field of functional organic conjugated molecular materials, and particularly relates to an organic conjugated compound with a naphtho-fused Aza-BODIPY as the basic skeleton, a preparation method thereof, and an application thereof. Background Art

[0002] As a near-infrared organic fluorescent dye, Aza-BODIPY dye molecules have extensive applications in the fields of optoelectronic devices, bioimaging, photodynamic therapy, etc. In the prior art, in order to improve the optoelectronic properties of such molecular materials, heavy atoms are introduced into the organic conjugated compounds with Aza-BODIPY as the basic skeleton. The introduction of heavy atoms will lead to a decrease in their fluorescence quantum yield and the production ability of reactive oxygen species. Moreover, in the synthesis process of the organic conjugated compounds with Aza-BODIPY as the basic skeleton, the intermediate synthesis route is complex and the structure is unstable, and the yield of the target product is relatively low, which is not conducive to large-scale preparation and application. Summary of the Invention

[0003] The purpose of the present invention is to overcome the problem in the prior art that the introduction of heavy atoms into the organic conjugated compounds with Aza-BODIPY as the basic skeleton leads to a decrease in their fluorescence quantum yield, and at the same time, it also overcomes the problems that in the synthesis process of the organic conjugated compounds with Aza-BODIPY as the basic skeleton, the intermediate synthesis route is complex and the structure is unstable, and the yield of the target product is relatively low, which is not conducive to large-scale preparation and application.

[0004] To achieve the above purpose, on the one hand, the present invention provides an organic conjugated compound with Aza-BODIPY as the basic skeleton, and the structure of the organic conjugated compound is shown in formula (G):

[0005]

[0006] Wherein, R1 is C1-C 12 alkyl; R2 is C1-C 12 alkoxy, halogen or hydrogen.

[0007] On the second aspect, the present invention provides a method for preparing the above-mentioned organic conjugated compound with Aza-BODIPY as the basic skeleton, and the method includes:

[0008] S1. In the presence of an inorganic base and a first alcohol solvent, contacting the benzocyclohexanone compound shown in formula (A) with the benzaldehyde compound shown in formula (B) to carry out a first reaction (aldol condensation reaction) to obtain the compound shown in formula (C);

[0009] S2. In the presence of a first organic base and a second alcohol solvent, the compound represented by formula (C) is contacted with nitromethane to carry out a second reaction (Michael addition) to obtain a compound represented by formula (D);

[0010] S3. In the presence of a third alcohol solvent, the compound represented by formula (D) is contacted with ammonium acetate to carry out a third reaction to obtain a compound represented by formula (E);

[0011] S4. In the presence of 1,2-dichloroethane and a second organic base, the compound represented by formula (E) is contacted with boron trifluoride diethyl ether to carry out a fourth reaction to obtain a compound represented by formula (F);

[0012] S5. In the presence of chloroform, the compound represented by formula (F) is contacted with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone to carry out a fifth reaction to obtain a compound represented by formula (G);

[0013]

[0014] The third aspect of the present invention provides an application of the above-mentioned organic conjugate compound with a naphtho-fused Aza-BODIPY as the basic skeleton as a fluorescent material, and the absorption wavelength of the organic conjugate compound is 300-900 nm.

[0015] Compared with the prior art, the present invention has the following technical effects: The present invention provides a novel Aza-BODIPY molecule with a β-naphtho-fused ring. The present invention overcomes the problem of difficulty in constructing a fused ring at the β-position in the Aza-BODIPY molecular structure in the prior art, provides a synthesis method of an Aza-BODIPY molecule with a β-naphtho-fused ring, and the method is simple. By introducing a fused ring structure, the absorption and emission wavelengths of the molecule can be further red-shifted, which can meet the requirements of near-infrared applications. And introducing a fused ring structure can increase the intermolecular interaction, thereby improving the optoelectronic properties of this type of molecular material.

[0016] Other features and advantages of the present invention will be described in detail in the subsequent specific implementation section. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The drawings are used to provide a further understanding of the present invention, and constitute a part of the specification, and are used to explain the present invention together with the following specific implementation manners, but do not constitute a limitation to the present invention. In the drawings:

[0018] Figure 1 is the absorption spectrum diagram of the compounds represented by formula (G1-G3) in dichloromethane in Test Example 1;

[0019] Figure 2 is the absorption spectrum diagram of the compound represented by formula G1 in different solvents in Test Example 1;

[0020] Figure 3 It is the absorption spectrum diagram of the compound shown in Formula G2 in Test Example 1 in different solvents;

[0021] Figure 4 It is the absorption spectrum diagram of the compound shown in Formula G3 in Test Example 1 in different solvents;

[0022] Figure 5 It is the hydrogen spectrum diagram of Formula G1 in Test Example 2;

[0023] Figure 6 It is the carbon spectrum diagram of Formula G1 in Test Example 2;

[0024] Figure 7 It is the hydrogen spectrum diagram of Formula G2 in Test Example 2;

[0025] Figure 8 It is the carbon spectrum diagram of Formula G2 in Test Example 2;

[0026] Figure 9 It is the hydrogen spectrum diagram of Formula G3 in Test Example 2;

[0027] Figure 10 It is the mass spectrum diagram of Formula G1 in Test Example 3;

[0028] Figure 11 It is the mass spectrum diagram of Formula G2 in Test Example 3;

[0029] Figure 12 It is the mass spectrum diagram of Formula G3 in Test Example 3. Detailed implementation manners

[0030] In order to make the technical means, creative features, achieved purposes and functions of the present invention easy to understand, the present invention will be further clarified below with reference to specific embodiments.

[0031] The present invention provides an organic conjugated compound with a naphtho-fused Aza-BODIPY as the basic skeleton, and the structure of the organic conjugated compound is shown in Formula (G):

[0032]

[0033] Among them, R1 is a C1-C 12 alkyl group; R2 is a C1-C 12 alkoxy group, halogen or hydrogen.

[0034] The present invention also provides a method for preparing an organic conjugated compound with an Aza-BODIPY as the basic skeleton as described above, and the method includes:

[0035] S1. In the presence of an inorganic base and a first alcohol solvent, the compound represented by formula (A) and the compound represented by formula (B) are contacted to carry out a first reaction to obtain the compound represented by formula (C);

[0036] S2. In the presence of a first organic base and a second alcohol solvent, the compound represented by formula (C) and nitromethane are contacted to carry out a second reaction to obtain the compound represented by formula (D);

[0037] S3. In the presence of a third alcohol solvent, the compound represented by formula (D) and ammonium acetate are contacted to carry out a third reaction to obtain the compound represented by formula (E);

[0038] S4. In the presence of a second organic base, the compound represented by formula (E) and boron trifluoride diethyl ether are contacted to carry out a fourth reaction to obtain the compound represented by formula (F);

[0039] S5. In the presence of chloroform, the compound represented by formula (F) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone are contacted to carry out a fifth reaction to obtain the compound represented by formula (G)

[0040]

[0041] In the above method, the amounts of the raw materials can be selected within a wide range. However, in order to further improve the fluorescence quantum yield and the ability to generate reactive oxygen species of the prepared organic conjugate compound, preferably, the conditions of the first reaction include: the molar ratio of the compound represented by formula (A), the compound represented by formula (B) and the inorganic base is 1:(1 - 1.2):(1 - 3);

[0042] The conditions of the second reaction include: the molar ratio of the compound represented by formula (C), nitromethane and the first organic base is 1:(6 - 10):(1 - 6);

[0043] The conditions of the third reaction include: the molar ratio of the compound represented by formula (D) to ammonium acetate is 1:(10 - 30);

[0044] The conditions of the fourth reaction include: the molar ratio of the compound represented by formula (E), the second organic base and boron trifluoride diethyl ether is 1:(20 - 30):(20 - 30).

[0045] The conditions of the fifth reaction include: the molar ratio of the compound represented by formula (F) to 2,3-dichloro-5,6-dicyano-1,4-benzoquinone is 1:(2 - 10).

[0046] In the above method, the conditions of each reaction can be selected within a wide range. However, in order to further improve the fluorescence quantum yield and the ability to generate reactive oxygen species of the prepared organic conjugate compound, preferably, the conditions of the first reaction include: the temperature is 0 - 40 °C;

[0047] The conditions for the second reaction include: a temperature of 60 - 100 °C;

[0048] The conditions for the third reaction include: a temperature of 80 - 120 °C;

[0049] The conditions for the fourth reaction include: a temperature of 20 - 60 °C.

[0050] The conditions for the fifth reaction include: a temperature of 60 - 80 °C

[0051] In the above method, the type of inorganic base used in step S1 can be selected within a wide range. Preferably, the inorganic base is potassium hydroxide and / or sodium hydroxide.

[0052] In the above method, the types of the first organic base used in step S2 and the second organic base used in step S4 can be selected within a wide range. However, in order to further improve the fluorescence quantum yield and the ability to generate reactive oxygen species of the prepared organic conjugate compound, preferably, the first organic base and the second organic base are each independently selected from at least one of sodium ethoxide, potassium tert - butoxide, triethylamine, diethylamine, DBU, and piperidine.

[0053] In the above method, the types of the first alcohol solvent used in step S1, the second alcohol solvent used in step S2, and the third alcohol solvent used in step S3 can be selected within a wide range. Preferably, the first alcohol solvent, the second alcohol solvent, and the third alcohol solvent are each independently selected from at least one of methanol, ethanol, and isopropanol.

[0054] The present invention further provides an application of the organic conjugate compound with Aza - BODIPY as the basic skeleton as described above as a photosensitizer material. When the concentration of the organic conjugate compound is 0 - 1 mol / L, reactive oxygen species can be generated under light irradiation with a wavelength of 300 - 700 nm.

[0055] The present invention also further provides an application of the organic conjugate compound with Aza - BODIPY as the basic skeleton as described above as an absorption material. The absorption wavelength of the organic conjugate compound is 300 - 900 nm.

[0056] The present invention is described in detail below through specific examples.

[0057] In the following examples, all chemical reagents (chloroform, toluene, acetonitrile, methanol, tetrahydrofuran) are analytical - grade reagents. Unless otherwise specified, they are generally used directly without further treatment.

[0058] The reaction was monitored using a 0.25 - mm - thick fluorescent TLC plate and a ZF - 1 type triple - purpose ultraviolet analyzer;

[0059] 11H NMR and 13 13C NMR were performed using a Bruker AVANCE III Spectrometers 400 or a Bruker AVANCE III Spectrometers 500 MHz nuclear magnetic resonance spectrometer, with CDCl3 as the solvent;

[0060] The instrument used for absorption spectroscopy was a UV-2450 type ultraviolet spectrophotometer; the instrument used for fluorescence spectroscopy was an Edinburgh FlS-920 type fluorescence spectrometer.

[0061] Preparation Example 1

[0062]

[0063] This preparation example provides a method for preparing a compound represented by the structural formula G1, and the method includes the following steps:

[0064] S1. React a compound represented by formula (A1) with a compound represented by formula (B1) and potassium hydroxide in a molar ratio of 1:1:1 in the presence of methanol at 20 °C for 1 hour to obtain a compound represented by formula (C1);

[0065] S2. Mix the compound represented by formula (C1) with nitromethane and potassium tert-butoxide in a molar ratio of 1:6:1 in the presence of ethanol and react at 80 °C for 12 hours to obtain a compound represented by formula (D1);

[0066] S3. Mix the compound represented by formula (D1) with ammonium acetate in a molar ratio of 1:10 in the presence of ethanol and react at 80 °C for 24 hours to obtain a compound represented by formula (E1);

[0067] S4. Mix the compound represented by formula (E1) with triethylamine and boron trifluoride diethyl etherate in a molar ratio of 1:20:20 in the presence of 1,2-dichloroethane and react at 60 °C for 2 hours, and then purify to obtain a compound represented by formula (F1) (yield: 82%);

[0068] S5. Mix the compound represented by formula (F1) with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone in a molar ratio of 1:4 in the presence of chloroform and react at 60 °C for 12 hours, and then purify to obtain a compound represented by formula (G1) (yield: 72%).

[0069]

[0070] The characterization data of the compound represented by formula (G1) are as follows: 11H NMR (400 MHz, CDCl3, ppm) δ 9.37 (d, J = 8.4 Hz, 2H), 7.86 (d, J = 8.4 Hz, 4H), 7.72 - 7.61 (m, 8H), 7.55 (d, J = 8.4, 4H), 7.30 (d, J = 9.2 Hz, 2H), 1.41 (s, 18H). 13 13C NMR (100 MHz, CDCl3, ppm) δ 152.8, 151.8, 149.1, 139.8, 137.7, 131.6, 130.9, 129.6, 129.5, 129.3, 127.7, 126.4, 125.5, 123.5, 120.4, 34.9, 31.2. HRMS (ESI) Calcd. for C 44 H 39 BF2N3 + [M + H] + 658.3200, found 658.3198.

[0071] Preparation Example 2

[0072]

[0073] This preparation example provides a method for preparing the compound shown in Structural Formula G2, and the method includes the following steps:

[0074] S1. React the compound shown in Formula (A2) with the compound shown in Formula (B1) and potassium hydroxide in a molar ratio of 1:1:1 in the presence of methanol at 20 °C for 1 hour to obtain the compound shown in Formula (C2);

[0075] S2. Mix the compound shown in Formula (C2) with nitromethane and diethylamine in a molar ratio of 1:6:6, and react in the presence of methanol at 65 °C for 12 hours to obtain the compound shown in Formula (D2);

[0076] S3. Mix the compound shown in Formula (D2) with ammonium acetate in a molar ratio of 1:10, and react in the presence of ethanol at 80 °C for 24 hours to obtain the compound shown in Formula (E2);

[0077] S4. Mix the compound shown in Formula (E2) with triethylamine and boron trifluoride diethyl etherate in a molar ratio of 1:20:20 in the presence of 1,2 - dichloroethane, and react at 60 °C for 2 hours, and then purify to obtain the compound shown in Formula (F2) (yield: 78%).

[0078] S5. The compound shown in formula (F2) reacts with dichlorodicyanobenzoquinone at a molar ratio of 1:4 in the presence of chloroform at 60 °C for 12 hours, and the compound shown in formula (G2) is prepared by purification (yield: 62%).

[0079]

[0080] The characterization data of the compound shown in formula (G2) are as follows: 1 H NMR (400 MHz, CDCl3, ppm) δ 9.25 (d, J = 9.2 Hz, 2H), 7.82 (d, J = 8.4 Hz, 4H), 7.70 - 7.61 (m, 6H), 7.54 (d, J = 8.4 Hz, 4H), 7.21 (d, J = 8.8 Hz, 2H), 1.41 (s, 18H). 13 C NMR (100 MHz, CDCl3, ppm) δ 153.2, 151.0, 149.2, 140.3, 138.7, 137.2, 131.6, 130.8, 129.3, 129.0, 128.7, 128.1, 125.6, 125.3, 121.8, 121.7, 34.9, 31.2. HRMS (ESI) calcd. for C 44 H 37 BCl2F2N3 + [M + H] + : 726.2426, found 726.2421.

[0081] Preparation Example 3

[0082]

[0083] This preparation example provides a method for preparing the compound shown in structural formula G3, and the method includes the following steps:

[0084] S1. The compound shown in formula (A3) reacts with the compound shown in formula (B1) and potassium hydroxide at a molar ratio of 1:1:1 in the presence of methanol at 20 °C for 1 hour to obtain the compound shown in formula (C3);

[0085] S2. The compound shown in formula (C3) is mixed with nitromethane and diethylamine at a molar ratio of 1:6:6, and reacts in the presence of methanol at 65 °C for 12 hours to obtain the compound shown in formula (D3);

[0086] S3. The compound shown in formula (D3) is mixed with ammonium acetate at a molar ratio of 1:10, and reacts in the presence of ethanol at 80 °C for 24 hours to obtain the compound shown in formula (E3);

[0087] S4. The compound shown in formula (E3) reacts with triethylamine and boron trifluoride diethyl ether in a molar ratio of 1:20:20 in the presence of 1,2-dichloroethane at 60 °C for 2 hours, and is purified to obtain the compound shown in formula (F3) (yield: 68%).

[0088] S5. The compound shown in formula (F3) reacts with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone in a molar ratio of 1:4 in the presence of chloroform at 60 °C for 12 hours, and is purified to obtain the compound shown in formula (G3) (yield: 74%).

[0089]

[0090] The characterization data of the compound shown in formula (G3) are as follows: 1 H NMR (400 MHz, CDCl3, ppm) δ 9.31 (d, J = 9.6 Hz, 2H), 7.85 (d, J = 8.4 Hz, 4H), 7.62 (d, J = 9.6 Hz, 2H), 7.53 (d, J = 8.4 Hz, 4H), 7.30 (d, J = 8.8 Hz, 2H), 7.21 (d, J = 8.8 Hz, 2H), 7.12 (s, 2H), 4.00 (s, 6H) 1.40 (s, 18H). HRMS (ESI) calcd. For C 46 H 42 BF2N3O2 [M] + : 717.3338, found 717.3330.

[0091] Test Example 1: Absorption Spectrum Test

[0092] Weigh 1 - 1.5 mg of the compound shown in formula (G1 - G3) and dissolve it in 2 mL of chloroform. Then, dilute it with n-hexane, toluene, dichloromethane, tetrahydrofuran, and acetonitrile respectively to prepare solutions with a molar concentration of 10 -6 mol / L; conduct absorption spectrum tests respectively, and the absorption spectrum test results are as Figures 1-4 shown.

[0093] Overall Figure 1 , Figure 2 it shows that the compound shown in formula (G1) has absorption ability in the range of 300 - 900 nm.

[0094] Test Example 2: 1H NMR Test

[0095] Perform 1H NMR test and 13C NMR test on the products obtained in Preparation Examples 1, 2, and 3, namely the compounds shown in formula (G1 / G2 / G3). The original 1H NMR spectra and 13C NMR spectra are as Figures 3-9 shown.

[0096] Test Example 3: High-resolution Mass Spectrometry Test

[0097] The products obtained in Preparation Examples 1, 2, and 3, namely the compounds represented by formula (G1 / G2 / G3), were subjected to high-resolution mass spectrometry testing. The resulting high-resolution mass spectra are as shown in Figure 10 , Figure 11 , Figure 12 .

[0098] The foregoing has shown and described the basic principles, main features, and characteristics of the present invention. Those skilled in the art should understand that the present invention is not limited by the above-mentioned embodiments. The above-mentioned embodiments and the descriptions in the specification are only to illustrate the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention will have various changes and improvements, and these changes and improvements all fall within the scope of the present invention claimed. The scope of the present invention claimed is defined by the appended claims and their equivalents.

Claims

1. An organic conjugated compound with naphthocyclic Aza-BODIPY as a basic skeleton, characterized in that: The structure of the organic conjugated compound is shown in formula (G): Where R1 is C1-C 12 Alkyl; R2 is C1-C 12 Alkoxy, halogen or hydrogen.

2. The organic conjugated compound according to claim 1, characterized in that R1 is tert-butyl, and R2 is selected from methoxy, chlorine or hydrogen.

3. A method for preparing an organic conjugated compound with naphthocyclic Aza-BODIPY as a basic skeleton as claimed in any one of claims 1 to 2, characterized in that: The method comprises: S1. In the presence of an inorganic base and a first alcohol solvent, contacting a benzocyclohexanone compound represented by formula (A) and a benzaldehyde compound represented by formula (B) to perform a first reaction (aldol condensation reaction) to obtain a compound represented by formula (C); S2. In the presence of a first organic base and a second alcohol solvent, contacting the compound represented by formula (C) with nitromethane to carry out a second reaction (Michael addition) to obtain a compound represented by formula (D); S3, in the presence of a third alcohol solvent, contacting the compound represented by formula (D) with ammonium acetate to carry out a third reaction to obtain a compound represented by formula (E); S4, in the presence of 1,2-dichloroethane and a second organic base, contacting the compound represented by formula (E) with boron trifluoride etherate to carry out a fourth reaction to obtain a compound represented by formula (F); S5. In the presence of chloroform, the compound represented by formula (F) is contacted with dichlorodicyanobenzoquinone to carry out a fifth reaction to obtain a compound represented by formula (G); 4. The method according to claim 3, characterized in that The conditions of the first reaction include: the molar ratio of the compound represented by formula (A), the compound represented by formula (B) and the inorganic base is 1:(1-1.2):(1-3).

5. The method according to claim 3, characterized in that: The conditions of the second reaction include: the molar ratio of the compound represented by formula (C), nitromethane and the first organic base is 1:(6-10):(1-6).

6. The method according to claim 3, characterized in that The conditions of the third reaction include: the molar ratio of the compound represented by formula (D) to ammonium acetate is 1:(10-30).

7. The method according to claim 3, characterized in that The conditions of the fourth reaction include: the molar ratio of the compound represented by formula (E), the second organic base and boron trifluoride etherate is 1:(20-30):(20-30).

8. The method according to claim 3, characterized in that The conditions of the fifth reaction include: the molar ratio of the compound represented by formula (F) to dichlorodicyanobenzoquinone is 1:(2-10).

9. The method according to claim 3, characterized in that: The conditions of the first reaction include: a temperature of 0-40°C; Preferably, the conditions of the second reaction include: a temperature of 60-100°C; Preferably, the conditions of the third reaction include: a temperature of 80-120°C; Preferably, the conditions of the fourth reaction include: a temperature of 20-60°C; Preferably, the conditions of the fifth reaction include: a temperature of 60-80°C Preferably, the inorganic base is potassium hydroxide and / or sodium hydroxide; Preferably, the first organic base and the second organic base are each independently selected from at least one of sodium ethoxide, potassium tert-butoxide, triethylamine, diethylamine, DBU and piperidine; Preferably, the first alcohol solvent, the second alcohol solvent and the third alcohol solvent are each independently selected from at least one of methanol, ethanol and isopropanol.

10. Use of the organic conjugated compound according to any one of claims 1 to 2 or the organic conjugated compound prepared by the method according to any one of claims 3 to 9 as an organic dye, characterized in that: The absorption wavelength of the organic conjugated compound is 300-900nm.

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